Lid cooling mechanism and method for optimized deposition of low-K dielectric using TRI methylsilane-ozone based processes

ABSTRACT

An apparatus and method for depositing thin films. The apparatus generally comprises a process chamber having one or more walls and a lid and two heat exchangers. A first heat exchanger is coupled to the walls and a second heat exchanger is coupled to the lid. The two heat exchangers are configured to provide separate temperature control of the walls and lid. Separate control of the lid and wall temperatures inhibits reaction of the organosilane within the lid while optimizing a reaction within the chamber. The apparatus implements a method, in which a process gas comprising ozone and an organosilane are admitted through the into a processing while a substrate is heated to form a carbon-doped silicon oxide layer over the substrate. During deposition, the lid is kept cooler than the walls.

CROSS REFERENCE TO RELATED APPLICATIONS

[0001] This application is related to related to concurrently filed U.S.application Ser. No. 09/______ entitled “THERMAL CVD PROCESS FORDEPOSITING A LOW DIELECTRIC CONSTANT CARBON-DOPED SILICON OXIDE FILM,”having Li-Qun Xia, Fabrice Geiger, Frederic Gaillard, Ellie Yieh andTian Lim as coinventors; and to concurrently filed U.S. application Ser.No. 09/______ entitled “SURFACE TREATMENT OF C-DOPED SIO₂ FILM TOENHANCE FILM STABILITY DURING O₂ ASHING,” having Li-Qun Xia, FredericGaillard, Ellie Yieh and Tian H. Lim as coinventors; and to concurrentlyfiled U.S. application Ser. No. 09/______ entitled “METHOD AND APPARATUSTO ENHANCE PROPERTIES OF Si—O—C LOW K FILMS,” having Li-Qun Xia,Frederic Gaillard, Ellie Yieh and Tian H. Lim as coinventors; and toconcurrently filed U.S. application Ser. No. 09/______ entitled“POST-DEPOSITION TREATMENT TO ENHANCE PROPERTIES OF Si—O—C LOW K FILMS,”having Li-Qun Xia, Frederic Gaillard, Ellie Yieh and Tian H. Lim ascoinventors. Each of the Ser. Nos. 09/______, 09/______, 09/______ and09/______ applications listed above are assigned to Applied Materials,Inc., the assignee of the present invention and each of theabove-referenced applications are hereby incorporated by reference.

BACKGROUND OF THE INVENTION

[0002] The present invention relates to the formation of dielectriclayers during fabrication of integrated circuits on semiconductorwafers. More particularly, the present invention relates to a method forproviding a dielectric film having a low dielectric constant that isparticularly useful as a premetal or intermetal dielectric layer.

[0003] One of the primary steps in the fabrication of modernsemiconductor devices is the formation of a thin film on a semiconductorsubstrate by chemical reaction of gases. Such a deposition process isreferred to as chemical vapor deposition or “CVD.” Conventional thermalCVD processes supply reactive gases to the substrate surface whereheat-induced chemical reactions take place to produce a desired film.Plasma enhanced CVD techniques, on the other hand, promote excitationand/or dissociation of the reactant gases by the application of radiofrequency (RF) or microwave energy. The high reactivity of the releasedspecies reduces the energy required for a chemical reaction to takeplace, and thus lowers the required temperature for such PECVDprocesses.

[0004] Semiconductor device geometries have dramatically decreased insize since such devices were first introduced several decades ago.Today's fabrication plants are routinely producing devices having 0.25μm and even 0.18 μm feature sizes, and tomorrow's plants soon will beproducing devices having even smaller geometries. In order to furtherreduce the size of devices on integrated circuits, it has becomenecessary to use conductive materials having low resistivity andinsulators having a low dielectric constant. Low dielectric constantfilms are particularly desirable for premetal dielectric (PMD) layersand intermetal dielectric (IMD) layers to reduce the RC time delay ofthe interconnect metalization, to prevent cross-talk between thedifferent levels of metalization, and to reduce device powerconsumption. Undoped silicon oxide films deposited using conventionalCVD techniques may have a dielectric constant (k) as low as about 4.0 or4.2. One approach to obtaining a lower dielectric constant is toincorporate fluorine in the silicon oxide film. Fluorine-doped siliconoxide films (also referred to as fluorine silicate glass or—“FSG” films)may have a dielectric constant as low as about 3.4 or 3.6. Despite thisimprovement, films having even lower dielectric constants are highlydesirable for the manufacture of integrated circuits using geometries of0.1 8 μm and smaller. Numerous films have been developed in attempts tomeet these needs including: a spin-on glass called HSQ (hydrogensilsesqui-oxane, HSiO_(1.5)) and various carbon-based dielectric layers,such as parylene and amorphous fluorinated carbon. Other low-k filmshave been deposited by CVD using an organosilane precursor and oxygen toform a silicon-oxygen-carbon (Si—O—C) layer.

[0005] While the above types of dielectric films are useful for someapplications, manufacturers are always seeking new and improved methodsof depositing low-k materials for use as IMD and other types ofdielectric layers. For example, in some applications, it is desirable toheat the walls of the chamber in which deposition takes place in orderto optimize the deposition reaction. Unfortunately this can cause theorganosilane to react undesirably before reaching the chamber, therebyreducing the deposition rate.

SUMMARY OF THE INVENTION

[0006] The disadvantages associated with the prior art are overcome byan apparatus and method for depositing thin films. The apparatusgenerally comprises a process chamber having one or more walls and a lidand two heat exchangers. A first heat exchanger is coupled to the wallsand a second heat exchanger is coupled to the lid. The two heatexchangers are configured to provide separate temperature control of thewalls and lid of the chamber. In one embodiment, the first heatexchanger is coupled to a first plurality of passages in the walls andthe second heat exchanger is coupled to a second plurality of passagesin the lid. Heat transfer is effected by fluids circulating with thepassages. The apparatus may further comprise a gas delivery systemhaving a gas distribution manifold attached to the lid and a substrateholder with a heater. Such a configuration is desirable in an apparatusfor depositing thin films with organosilanes. Separate control of thelid and wall temperatures inhibits reaction of the organosilane withinthe gas distribution manifold while optimizing reaction of theorganosilane within the chamber.

[0007] The method of the present invention deposits a carbon-dopedsilicon oxide layer using a thermal, as opposed to plasma, CVD process.The substrate can be heated during densification. The method isparticularly suitable for deposition of low dielectric constant filmsusing methylsilane or di-, tri-, tetra-, or phenylmethylsilane andozone. In one embodiment, the layer is deposited from a process gas ofozone and an organosilane precursor having at least one silicon-carbon(Si—C) bond. During the deposition process, the substrate is heated to atemperature less than about 250° C. In some embodiments, theorganosilane precursor has a formula of Si(CH₃)_(x)H_(4−x) where x iseither 3 or 4 making the organosilane precursor either trimethylsilane(TMS) or tetramethylsilane (T4MS). In one specific embodiment, theprocess gas is a mixture of TMS, ozone and helium to deposit a low kcarbon-doped silicon oxide film. In other embodiments, the substrateover which the carbon-doped oxide layer is deposited is heated to atemperature of between about 100-200° C. and the deposition is carriedout in a vacuum chamber at a pressure of between 1-760 Torr. In stillother embodiments, the carbon-doped silicon oxide layer is cured afterit is deposited to minimize subsequent moisture absorption. Curing canbe done in either a vacuum or conventional furnace environment.

[0008] The above-described apparatus can be incorporated into asubstrate processing system directed by a controller operating under thedirection of a computer program. The system and apparatus can implementthe method for forming a layer of material over a substrate.

[0009] The apparatus, method, and processing system are particularlyuseful in the manufacture of sub-0.2 micron circuits as it can form aPMD or IMD film with a dielectric constant below 3.0. The film has goodgap fill capabilities, high film stability and etches uniformly andcontrollably when subject to a chemical mechanical polishing (CMP) step.

[0010] These and other embodiments of the present invention, as well asits advantages and features, are described in more detail in conjunctionwith the text below and attached figures.

BRIEF DESCRIPTION OF THE DRAWINGS

[0011]FIGS. 1A and 1B are vertical, cross-sectional views of oneembodiment of a chemical vapor deposition apparatus according to thepresent invention;

[0012]FIGS. 1C and 1D are exploded perspective views of parts of the CVDchamber depicted in FIG. 1A;

[0013]FIG. 1E is a simplified diagram of system monitor and CVD system10 in a multi-chamber system, which may include one or more chambers;

[0014]FIG. 1F shows an illustrative block diagram of the hierarchicalcontrol structure of the system control software, computer program 70,according to a specific embodiment;

[0015]FIG. 2 is a simplified vertical cross sectional diagram of a CVDapparatus according to an alternative embodiment of the presentinvention;

[0016]FIG. 3 is a flowchart illustrating the formation of a carbon-dopedsilicon oxide layer according to one embodiment of the method of thepresent invention;

[0017]FIG. 4 is a graph of substrate temperature versus dielectricconstant for a carbon-doped silicon oxide film deposited in accordancewith a particular embodiment of the present invention;

[0018]FIG. 5 is a graph showing the effect of substrate temperature ondeposition rate for a carbon-doped silicon oxide film deposited inaccordance with a particular embodiment of the present invention;

[0019] FIGS. 6A-C are drawings illustrating the gap fill capabilities offilms deposited according to the present invention at depositiontemperatures of 150-250° C.;

[0020]FIG. 7 is a graph showing the effect of an inert gas flow ofhelium on film uniformity in a carbon-doped silicon oxide film depositedaccording to the present invention;

[0021]FIGS. 8A and 8B are graphs of FTIR data that compare thecrystalline orientation of a carbon-doped silicon oxide film depositedand cured according to the present invention with an uncured film;

[0022]FIG. 9 is a flowchart of one process according to the presentinvention that employs a process gas of TMS, ozone and helium;

[0023]FIG. 10 is a flowchart illustrating the integration of theformation of a carbon-doped silicon oxide layer according to anembodiment of the method of the present invention;

[0024]FIG. 11a is a cross sectional view of an integrated circuitstructure undergoing sputtering;

[0025]FIG. 11b is a cross sectional view of an integrated circuitstructure undergoing treatment with free atomic hydrogen;

[0026]FIG. 12a depicts a remote RF plasma source according to anembodiment of the present invention;

[0027]FIG. 12b depicts a remote microwave plasma source according toanother embodiment of the present invention;

[0028]FIGS. 13a-13 e depict FTIR spectra for carbon-doped silicon oxidefilms;

[0029]FIGS. 14a-14 f depict flow diagrams illustrating the integrationenhancements to formation of a carbon-doped silicon oxide layeraccording to another embodiment of the method of the present invention;

[0030]FIGS. 15a-15 h depict a cross section of a partially formedintegrated circuit undergoing integrated processing according to anembodiment of the present invention; and

[0031]FIGS. 16a-16 h depict a cross-section of a partially formedintegrated circuit undergoing an integrated dual-damascene processaccording to an embodiment of the present invention.

DESCRIPTION OF THE SPECIFIC EMBODIMENTS

[0032] I. Exemplary CVD System

[0033] One suitable CVD apparatus in which the method of the presentinvention can be carried out is shown in FIGS. 1A and 1B, which arevertical, cross-sectional views of a CVD system 10, having a vacuum orprocessing chamber 15 that includes a chamber wall 15 a and chamber lidassembly 15 b. Chamber wall 15 a and chamber lid assembly 15 b are shownin exploded, perspective views in FIGS. 1C and 1D.

[0034] CVD system 10 contains a gas distribution manifold 11 fordispersing process gases to a substrate (not shown) that rests on aheated pedestal 12 centered within the process chamber. Duringprocessing, the substrate (e.g. a semiconductor wafer) is positioned ona flat (or slightly convex) surface 12 a of pedestal 12. The pedestalcan be moved controllably between a lower loading/off-loading position(depicted in FIG. 1A) and an upper processing position (indicated bydashed line 14 in FIG. 1A and shown in FIG. 1B), which is closelyadjacent to manifold 11. A centerboard (not shown) includes sensors forproviding information on the position of the wafers.

[0035] Deposition and carrier gases are introduced into chamber 15through perforated holes 13 b (FIG. 1D) of a conventional flat, circulargas distribution or faceplate 13 a. More specifically, depositionprocess gases flow into the chamber through the inlet manifold 11(indicated by arrow 40 in FIG. 1B), through a conventional perforatedblocker plate 42 and then through holes 13 b in gas distributionfaceplate 13 a.

[0036] Before reaching the manifold, deposition and carrier gases areinput from gas sources 7 through gas supply lines 8 (FIG. 1B) into amixing system 9 where they are combined and then sent to manifold 11.Generally, the supply line for each process gas includes (i) severalsafety shut-off valves (not shown) that can be used to automatically ormanually shut-off the flow of process gas into the chamber, and (ii)mass flow controllers (also not shown) that measure the flow of gasthrough the supply line. When toxic gases are used in the process, theseveral safety shut-off valves are positioned on each gas supply line inconventional configurations.

[0037] The deposition process performed in CVD system 10 can be either athermal process or a plasma-enhanced process. In a plasma-enhancedprocess, an RF power supply 44 applies electrical power between the gasdistribution faceplate 13 a and the pedestal so as to excite the processgas mixture to form a plasma within the cylindrical region between thefaceplate 13 a and the pedestal. (This region will be referred to hereinas the “reaction region”). Constituents of the plasma react to deposit adesired film on the surface of the semiconductor wafer supported onpedestal 12. RF power supply 44 is a mixed frequency RF power supplythat typically supplies power at a high RF frequency (RF1) of 13.56 MHzand at a low RF frequency (RF2) of 450 KHz to enhance the decompositionof reactive species introduced into the vacuum chamber 15. In a thermalprocess, RF power supply 44 would not be utilized, and the process gasmixture thermally reacts to deposit the desired films on the surface ofthe semiconductor wafer supported on pedestal 12, which is resistivelyheated to provide thermal energy for the reaction.

[0038] During a thermal deposition process, a heat transfer liquid iscirculated through the walls 15 a of the process chamber to maintain thechamber at a constant temperature to prevent condensation of liquidprecursors and reduce gas phase reactions that could create particles. Aportion of these heat-exchanging passages in the lid of chamber 15(passages 18) is shown in FIG. 1B. The passages in the remainder ofchamber walls 15 a are not shown. Fluids used to heat the chamber walls15 a include the typical fluid types, i.e., water-based ethylene glycolor oil-based thermal transfer fluids. This heating (referred to asheating by the “heat exchanger”) beneficially reduces or eliminatescondensation of undesirable reactant products and improves theelimination of volatile products of the process gases and othercontaminants that might contaminate the process if they were to condenseon the walls of cool vacuum passages and migrate back into theprocessing chamber during periods of no gas flow.

[0039] The remainder of the gas mixture that is not deposited in alayer, including reaction byproducts, is evacuated from the chamber by avacuum pump (not shown). Specifically, the gases are exhausted throughan annular, slot-shaped orifice 16 surrounding the reaction region andinto an annular exhaust plenum 17. The annular slot 16 and the plenum 17are defined by the gap between the top of the chamber's cylindricalside-wall 15 a (including the upper dielectric lining 19 on the wall)and the bottom of the circular chamber lid 20. The 360° circularsymmetry and uniformity of the slot orifice 16 and the plenum 17 helpachieve a uniform flow of process gases over the wafer so as to deposita uniform film on the wafer.

[0040] From the exhaust plenum 17, the gases flow underneath a lateralextension portion 21 of the exhaust plenum 17, past a viewing port (notshown), through a downward-extending gas passage 23, past a vacuumshut-off valve 24 (whose body is integrated with the lower chamber wall15 a), and into the exhaust outlet 25 that connects to the externalvacuum pump (not shown) through a foreline (also not shown).

[0041] The wafer support platter of the pedestal 12 (preferablyaluminum, ceramic, or a combination thereof) is resistively-heated usingan embedded single-loop embedded heater element configured to make twofull turns in the form of parallel concentric circles. An outer portionof the heater element runs adjacent to a perimeter of the supportplatter, while an inner portion runs on the path of a concentric circlehaving a smaller radius. The wiring to the heater element passes throughthe stem of the pedestal 12. Typically, any or all of the chamberlining, gas inlet manifold faceplate, and various other reactor hardwareare made out of material such as aluminum, anodized aluminum, orceramic. An example of such a CVD apparatus is described in U.S. Pat.No. 5,558,717 entitled “CVD Processing Chamber,” issued to Zhao et al.The U.S. Pat. No. 5,558,717 patent is assigned to Applied Materials,Inc., the assignee of the present invention, and is hereby incorporatedby reference in its entirety.

[0042] A lift mechanism and motor 32 (FIG. 1A) raises and lowers theheater pedestal assembly 12 and its wafer lift pins 12 b as wafers aretransferred into and out of the body of the chamber by a robot blade(not shown) through an insertion/removal opening 26 in the side of thechamber 15. The motor 32 raises and lowers pedestal 12 between aprocessing position 14 and a lower, wafer-loading position. The motor,valves or flow controllers connected to the supply lines 8, gas deliverysystem, throttle valve, RF power supply 44, and chamber, substrateheating system and heat exchangers H1, H2 are all controlled by a systemcontroller 34 (FIG. 1B) over control lines 36, of which only some areshown. Controller 34 relies on feedback from optical sensors todetermine the position of movable mechanical assemblies such as thethrottle valve and susceptor which are moved by appropriate motors underthe control of controller 34.

[0043] In a preferred embodiment, the system controller includes a harddisk drive (memory 38), a floppy disk drive and a processor 37. Theprocessor contains a single-board computer (SBC), analog and digitalinput/output boards, interface boards and stepper motor controllerboards. Various parts of CVD system 10 conform to the Versa ModularEuropean (VME) standard which defines board, card cage, and connectordimensions and types. The VME standard also defines the bus structure ashaving a 16-bit data bus and a 24-bit address bus.

[0044] System controller 34 controls all of the activities of the CVDmachine. The system controller executes system control software, whichis a computer program stored in a computer-readable medium such as amemory 38. Preferably, memory 38 is a hard disk drive, but memory 38 mayalso be other kinds of memory. The computer program includes sets ofinstructions that dictate the timing, mixture of gases, chamberpressure, chamber temperature, RF power levels, susceptor position, andother parameters of a particular process. Other computer programs storedon other memory devices including, for example, a floppy disk or otheranother appropriate drive, may also be used to operate controller 34.

[0045] The interface between a user and controller 34 is via a CRTmonitor 50 a and light pen 50 b, shown in FIG. 1E, which is a simplifieddiagram of the system monitor and CVD system 10 in a substrateprocessing system, which may include one or more chambers. In thepreferred embodiment two monitors 50 a are used, one mounted in theclean room wall for the operators and the other behind the wall for theservice technicians. The monitors 50 a simultaneously display the sameinformation, but only one light pen 50 b is enabled. A light sensor inthe tip of light pen 50 b detects light emitted by CRT display. Toselect a particular screen or function, the operator touches adesignated area of the display screen and pushes the button on the pen50 b. The touched area changes its highlighted color, or a new menu orscreen is displayed, confirming communication between the light pen andthe display screen. Other devices, such as a keyboard, mouse, or otherpointing or communication device, may be used instead of or in additionto light pen 50 b to allow the user to communicate with controller 34.

[0046] The process for depositing the film can be implemented using acomputer program product that is executed by controller 34. The computerprogram code can be written in any conventional computer readableprogramming language: for example, 68000 assembly language, C, C++,Pascal, Fortran or others. Suitable program code is entered into asingle file, or multiple files, using a conventional text editor, andstored or embodied in a computer usable medium, such as a memory systemof the computer. If the entered code text is in a high level language,the code is compiled, and the resultant compiler code is then linkedwith an object code of precompiled Windows™ library routines. To executethe linked, compiled object code the system user invokes the objectcode, causing the computer system to load the code in memory. The CPUthen reads and executes the code to perform the tasks identified in theprogram.

[0047]FIG. 1F is an illustrative block diagram of the hierarchicalcontrol structure of the system control software, computer program 70,according to a specific embodiment. Using the light pen interface, auser enters a process set number and process chamber number into aprocess selector subroutine 73 in response to menus or screens displayedon the CRT monitor. The process sets are predetermined sets of processparameters necessary to carry out specified processes, and areidentified by predefined set numbers. The process selector subroutine 73identifies (i) the desired process chamber and (ii) the desired set ofprocess parameters needed to operate the process chamber for performingthe desired process. The process parameters for performing a specificprocess relate to process conditions such as, for example, process gascomposition and flow rates, temperature, pressure, plasma conditionssuch as RF power levels and the low frequency RF frequency, cooling gaspressure, and chamber wall temperature. These parameters are provided tothe user in the form of a recipe, and are entered utilizing the lightpen/CRT monitor interface.

[0048] The signals for monitoring the process are provided by the analogand digital input boards of the system controller, and the signals forcontrolling the process are output on the analog and digital outputboards of CVD system 10.

[0049] A process sequencer subroutine 75 comprises program code foraccepting the identified process chamber and set of process parametersfrom the process selector subroutine 73, and for controlling operationof the various process chambers. Multiple users can enter process setnumbers and process chamber numbers, or a user can enter multipleprocess set numbers and process chamber numbers, so the sequencersubroutine 75 operates to schedule the selected processes in the desiredsequence. Preferably, the sequencer subroutine 75 includes a programcode to perform the steps of (i) monitoring the operation of the processchambers to determine if the chambers are being used, (ii) determiningwhat processes are being carried out in the chambers being used, and(iii) executing the desired process based on availability of a processchamber and type of process to be carried out. Conventional methods ofmonitoring the process chambers can be used, such as polling. Whenscheduling which process is to be executed, sequencer subroutine 75takes into consideration the present condition of the process chamberbeing used in comparison with the desired process conditions for aselected process, or the “age” of each particular user entered request,or any other relevant factor a system programmer desires to include fordetermining scheduling priorities.

[0050] Once the sequencer subroutine 75 determines which process chamberand process set combination is going to be executed next, the sequencersubroutine 75 initiates execution of the process set by passing theparticular process set parameters to a chamber manager subroutine 77a-c, which controls multiple processing tasks in a process chamber 15according to the process set determined by the sequencer subroutine 75.For example, the chamber manager subroutine 77 a comprises program codefor controlling sputtering and CVD process operations in the processchamber 15. The chamber manager subroutine 77 also controls execution ofvarious chamber component subroutines that control operation of thechamber components necessary to carry out the selected process set.Examples of chamber component subroutines are substrate positioningsubroutine 80, process gas control subroutine 83, pressure controlsubroutine 85, heater control subroutine 87, and plasma controlsubroutine 90. Those having ordinary skill in the art will readilyrecognize that other chamber control subroutines can be includeddepending on what processes are to be performed in the process chamber15. In operation, the chamber manager subroutine 77 a selectivelyschedules or calls the process component subroutines in accordance withthe particular process set being executed. The chamber managersubroutine 77 a schedules the process component subroutines much likethe sequencer subroutine 75 schedules which process chamber 15 andprocess set are to be executed next. Typically, the chamber managersubroutine 77 a includes steps of monitoring the various chambercomponents, determining which components need to be operated based onthe process parameters for the process set to be executed, and causingexecution of a chamber component subroutine responsive to the monitoringand determining steps.

[0051] Operation of particular chamber component subroutines will now bedescribed with reference to FIG. 1F. The substrate positioningsubroutine 80 comprises program code for controlling chamber componentsthat are used to load the substrate onto pedestal 12 and, optionally, tolift the substrate to a desired height in the chamber 15 to control thespacing between the substrate and the gas distribution manifold 11. Whena substrate is loaded into the process chamber 15, pedestal 12 islowered to receive the substrate, and thereafter, the susceptor 12 israised to the desired height in the chamber, to maintain the substrateat a first distance or spacing from the gas distribution manifold duringthe CVD process. In operation, the substrate positioning subroutine 80controls movement of pedestal 12 in response to process set parametersrelated to the support height that are transferred from the chambermanager subroutine 77 a.

[0052] The process gas control subroutine 83 has program code forcontrolling process gas composition and flow rates. The process gascontrol subroutine 83 controls the open/close position of the safetyshut-off valves, and also ramps up/down the mass flow controllers toobtain the desired gas flow rate. The process gas control subroutine 83is invoked by the chamber manager subroutine 77 a, as are all chambercomponent subroutines, and receives from the chamber manager subroutineprocess parameters related to the desired gas flow rates. Typically, theprocess gas control subroutine 83 operates by opening the gas supplylines and repeatedly (i) reading the necessary mass flow controllers,(ii) comparing the readings to the desired flow rates received from thechamber manager subroutine 77 a, and (iii) adjusting the flow rates ofthe gas supply lines as necessary. Furthermore, the process gas controlsubroutine 83 includes steps for monitoring the gas flow rates forunsafe rates and for activating the safety shut-off valves when anunsafe condition is detected.

[0053] In some processes, an inert gas such as helium or argon is flowedinto the chamber 15 to stabilize the pressure in the chamber beforereactive process gases are introduced. For these processes, the processgas control subroutine 83 is programmed to include steps for flowing theinert gas into the chamber 15 for an amount of time necessary tostabilize the pressure in the chamber, and dilute the reactant so thatthere is a uniform reaction. Then the steps described above would becarried out. Additionally, when a process gas is to be vaporized from aliquid precursor, for example, tetraethylorthosilane (“TEOS”), theprocess gas control subroutine 83 is written to include steps forbubbling a delivery gas, such as helium, through the liquid precursor ina bubbler assembly or introducing a carrier gas, such as helium ornitrogen, to a liquid injection system.

[0054] The pressure control subroutine 85 comprises program code forcontrolling the pressure in the chamber 15 by regulating the size of theopening of the throttle valve in the exhaust system of the chamber. Thesize of the opening of the throttle valve is set to control the chamberpressure to the desired level in relation to the total process gas flow,size of the process chamber, and pumping setpoint pressure for theexhaust system. When the pressure control subroutine 85 is invoked, thedesired, or target, pressure level is received as a parameter from thechamber manager subroutine 77 a. The pressure control subroutine 85operates to measure the pressure in the chamber 15 by reading one ormore conventional pressure manometers connected to the chamber, tocompare the measure value(s) to the target pressure, to obtain PID(proportional, integral, and differential) values from a stored pressuretable corresponding to the target pressure, and to adjust the throttlevalve according to the PID values obtained from the pressure table.Alternatively, the pressure control subroutine 85 can be written to openor close the throttle valve to a particular opening size to regulate thechamber 15 to the desired pressure.

[0055] The heater control subroutine 87 comprises program code forcontrolling the current to a heating unit that is used to heat thesubstrate 20 and/or the heat exchanger. The heater control subroutine 87is also invoked by the chamber manager subroutine 77 a and receives atarget, or set-point, temperature parameter. The heater controlsubroutine 87 measures the temperature by measuring voltage output of athermocouple located in pedestal 12 chamber 15, or lid assembly 15 a,comparing the measured temperature to the set-point temperature, andincreasing or decreasing current applied to the heating unit to obtainthe set-point temperature. The temperature is obtained from the measuredvoltage by looking up the corresponding temperature in a storedconversion table, or by calculating the temperature using a fourth-orderpolynomial. When, for example, an embedded loop is used to heat pedestal12, the heater control subroutine 87 gradually controls a ramp up/downof current applied to the loop. Additionally, a built-in fail-safe modecan be included to detect process safety compliance, and can shut downoperation of the heating unit if the process chamber 15 is not properlyset up.

[0056] The plasma control subroutine 90 comprises program code forsetting the low and high frequency RF power levels applied to theprocess electrodes in the chamber 15 and for setting the low frequencyRF frequency employed. Similar to the previously described chambercomponent subroutines, the plasma control subroutine 90 is invoked bythe chamber manager subroutine 77 a.

[0057] The above reactor description is mainly for illustrativepurposes, and other thermal CVD equipment such as the Giga-fill chambermanufactured by Applied Materials may be employed. Additionally,variations of the above-described system, such as variations in pedestaldesign, heater design, RF power frequencies, location of RF powerconnections and others are possible. For example, the wafer could besupported by a susceptor and heated by quartz lamps. The method of thepresent invention is not limited to any specific CVD apparatus.

[0058] II. Exemplary Deposition of an IMD Layer

[0059] Certain embodiments of the present invention relate to depositionof a carbon-doped silicon oxide low K film using a thermal CVD process.Other embodiments of the present invention enhance the adhesion andstability of thin films including carbon-doped silicon oxide filmsdeposited from an ozone/organosilane precursor gas according the methoddiscovered by the present inventors. Embodiments of the invention can bepracticed in a CVD deposition chamber such as the exemplary chamberdescribed above. Embodiments of the present invention related to thedeposition of a low k thermal CVD carbon-doped silicon oxide film areparticularly useful for the deposition of premetal and intermetaldielectric layers (sometimes referred to as interlevel dielectriclayers), especially those used for sub-0.2 micron applications.

[0060]FIG. 3 is a flowchart illustrating the formation of a carbon-dopedsilicon oxide layer according to one embodiment of the presentinvention. As shown in FIG. 3, the film is deposited by flowing anorganosilane precursor gas and ozone into a substrate processing chamberand heating the substrate within the chamber to a temperature less thanabout 250° C. (step 305). The deposition process is a thermal, asopposed to plasma, CVD process. After the film is deposited, it is thencured (step 310) to form a stable polymeric structure and increase itsresistance to moisture absorption. In order to form a film having asufficiently low dielectric constant, it is important that theorganosilane precursor gas used for film deposition have at least onesilicon-carbon bond. Examples of such precursor gases includemethylsilane, dimethylsilane (DMS), trimethylsilane (TMS),tetramethylsilane (T4MS) and phenylmethylsilane among others. Because oftheir commercial availability and high number of silicon-carbon bonds,TMS and T4MS are the currently most preferred precursor gases. Furtherdetails of the preferred deposition process conditions and preferredcuring processes are discussed in detail below.

[0061] The present inventors have found that the dielectric constant ofcarbon-doped silicon oxide film deposited in step 305 is directlyrelated to the temperature of the substrate during deposition. In orderto deposit a film having a dielectric constant that is sufficient forlow k applications (e.g., a k less than or equal to 3.0), it isimportant that the deposition temperature be kept below 250° C.Temperatures lower than 250° C. are preferred in other embodiments.

[0062] As used herein “deposition temperature” refers to the temperatureof the substrate during deposition. In the currently preferredembodiments, the substrate is directly heated by the pedestal heater. Athigher pressures, e.g., 200 Torr and above, the substrate temperature ispractically equal to the pedestal temperature (substrate temperature maybe about 10° C. less) due to conduction and convection heating. At nearvacuum pressures, however, (e.g., less than 50 Torr) there may be a50-60° C. temperature difference between the substrate and pedestalbecause of the lack of convection heating. Thus, at these lower pressurelevels, the pedestal temperature can be set up to 50-60° C. higher thanthe desired deposition temperature.

[0063]FIG. 4 is a graph showing the effect of temperature on dielectricconstant for a particular set of deposition conditions at a depositionpressure above 200 Torr. As shown in FIG. 4, a pedestal temperature of250° C. resulted in a dielectric constant of 4.6 while pedestaltemperatures of 200° C. and 150° C. resulted in dielectric constants of3.0 and 2.7 respectively. Thus, as evident from the figure and fromother tests the inventors ran, a temperature of 200° C. and below ispreferred. It is believed that the deposition temperature has a directeffect on the amount of carbon incorporated into the deposited film.Silicon oxide films having higher carbon concentration levels generallyhave a lower dielectric constant than silicon oxide films having lowercarbon levels, other dopant concentrations being similar. Filmsdeposited according to the present invention preferably have a carboncontent of at least 8 atomic percent and more preferably at least 10atomic percent.

[0064] Deposition temperature is also important, however, in achievinggas phase reactions between ozone and the organosilane precursor. Ozoneactivates through these gas phase collisions and a sufficiently hightemperature is required to ensure a commercially acceptable depositionrate. Thus, while it is important to have a sufficiently low depositiontemperature to obtain an appropriate low dielectric constant, this mustbe balanced against deposition rate. FIG. 5 is a graph showing theeffect of pedestal temperature on deposition rate. For FIG. 5 acarbon-doped silicon oxide film was deposited at a pressure of 200 Torrand spaced 250 mils from the gas distribution manifold. A process gas ofTMS (170 sccm), 12.5 wt. % ozone (1000 sccm and helium (6000 sccm) wasflowed into the chamber and the pedestal temperature was varied from150° C. to 350° C. As shown in FIG. 5, deposition rate increases as thepedestal temperature is increased. The activation energy of thereaction, however, is only 3.8 kcal/mol, indicating that the reactioncontrolling step is in the gas phase. In order to achieve a commerciallyacceptable deposition rate for IMD and PMD applications, it is useful tomaintain the pedestal temperature at about 100° C. or above. In anotherset of experiments and tests, the deposition rate of carbon-dopedsilicon oxide films was measured for pedestal temperature of 100° C.,150° C. and 200° C. In these tests, the 200° C. process had a depositionrate of about 1000 Å/min and the 150° C. process had a rate of about 500Å/min. Below 100° C., however, the process had a deposition rate ofabout 50 Å/min—a rate that is currently considered too low for practicalcommercial applications as an IMD or PMD layer. At depositiontemperatures sufficiently below 100° C. ozone may not be activated anddeposition may not occur at all.

[0065] A technique the inventors have devised to increase the depositionrate at a given pedestal temperature concerns heating at least the upperportion of the substrate processing chamber with the heat exchanger (thetemperature controlled liquid that circulates through passages in thechambers walls described in the exemplary chamber section). In mostconventional TEOS/ozone IMD deposition applications, the substrate isheated to a temperature of at least 400° C. In a cold wall reactor thisheating is done primarily by heating the substrate directly (i.e., witha heated pedestal). At such a relatively high deposition temperature,the effect of the heat exchanger on the deposition process is minimal.That is, the heat exchanger cannot alter process conditions in anysignificant manner to be thought of as an additional “control knob” forthe process.

[0066] The present inventors, however, have determined that because ofthe relatively low substrate temperatures that are preferred for thepresent invention, the heat exchanger can have a significant effect ondeposition rate. Specifically, the heat exchanger can be used as anadditional “control knob” to increase the deposition rate of thecarbon-doped silicon oxide film. The inventors have determined thatheating the glycol/water mixture to a temperature above the normallyrecommended temperature of 65° C. helps activate ozone in the gas phase,which in turn leads to an increased deposition rate for the growingfilm, a lower dielectric constant and better gap fill properties. Otherembodiments of the invention, use the heat exchanger to heat theglycol/water mixture to between 55 and 100° C.

[0067] In previously known systems only a single heat exchanger and heatexchange loop was coupled to passages 18 a and passages 18 b. Therefore,the walls 15 a and lid 15 b were kept at approximately the sametemperature. Since the temperature was chosen to optimize the depositionreaction in the chamber 15, organosilane precursor tended to reactbehind the blocker plate 42 in such a way as to choke off the flow ofgas through the gas distribution manifold 11. To, overcome this, thedeposition chamber can be configured to provide separate control of thetemperature of the chamber walls and the temperature of the chamber lidassembly. In one embodiment, depicted in FIG. 2, chamber 15 is equippedwith two heat exchangers H1 and H2 coupled to separate heat exchangeloops L1 and L2 respectively. Heat exchangers H1 and H2 mechanisms fortransfer of thermal energy to or from heat transfer medium, such asfluids circulating in heat exchange loops L1 and L2. Such thermal energytransfer can heat the fluid, e.g., resistively, conductively,convectively, radiatively or by exothermic chemical reaction.Alternatively, such thermal energy transfer can cool the fluid, e.g.,conductively, convectively, radiatively, evaporatively, by Peltiereffect or by endothermic chemical reaction.

[0068] Heat exchange loop L1 is coupled to passages 18 a in the walls 15a of chamber 15. Heat exchange loop L2 is coupled to passages 18 b inlid assembly 15 b, e.g., in gas distribution manifold 11. Loop L1 and L2are not fluidly coupled to each other. Thus it is possible, for exampleto heat walls 15 a while cooling lid assembly 15 b. This is useful when,for example, it is desired to optimize the reaction occurring withinchamber 15, while at the same time inhibiting reaction of reactants ingas distribution manifold, e.g., behind blocker plate 42. A specificexample of a suitable heat exchanger H1 is an AMAT-0 unit, manufacturedby Applied Materials of Santa Clara. Such a heat exchanger unit isgenerally capable of maintaining the chamber walls 15 a at between 45and 100° C. A specific example of heat exchanger H2 is a refrigeratedbath unit model AMAT RTE-140, manufactured by NESLAB of Portsmouth, N.H.Such a unit is generally capable of maintaining the 15 b at atemperature of between −40 and 100° C. Both units use a 50-50 mixture ofglycol and water as a heat transfer medium.

[0069] In one embodiment, heater control subroutine maintains thechamber walls 15 a at a temperature of approximately 60° C. and lidassembly 15 b at a temperature of approximately 25° C. during depositionof a low-k material with an organosilane precursor. Operating the systemin this manner inhibits thermal reaction of the precursor behind theblocker plate 42 and prevents choking of the flow of gas through the gasdistribution manifold 11. Consequently, the deposition rate can besubstantially increased compared to deposition performed with a singleheat exchanger coupled to both lid assembly 15 b and walls 15 a. Heatercontrol subroutine 87 can be configured to separately control heatexchangers H1 and H2.

[0070] The inventors have also determined that the gap fill propertiesof the carbon-doped silicon oxide film deposited according to thepresent invention are better at lower substrate deposition temperaturesas compared with higher deposition temperatures. FIGS. 6A-C are sketchesshowing the cross-sectional view of a film deposited according to thepresent invention over adjacent raised surfaces. FIG. 6A shows a filmdeposited at a pedestal temperature of 250° C., while the film in FIG.6B was deposited at 200° C. and the film in FIG. 6C was deposited at150° C. As shown in the figures, the gap fill capability of the 150° C.film is significantly better than the higher temperature films. Higherwall temperatures, however, improve the gap fill properties of the film.Specifically, in a dual heat exchange systems higher settings of heatexchange H1 operatively coupled to the walls encircling the substrateraise the wall temperatures. It is believed that these improvedproperties are due to the effect the heat exchanger has on ozoneactivation in the gas phase. Increasing the wall temperature leads to anincrease in the gas phase temperature as well as an increase in ozonedecomposition in the gas phase reaction.

[0071] While the overall deposition pressure can be varied between 1-760Torr to help obtain desired film properties, it is important that thepartial pressure of the organosilane precursor be kept below its vaporpressure in the deposition environment. The formula for partial pressureof the organosilane precursor is set forth as formula (1) below:

(Organosilane Flow/Total Gas Flow)×Chamber Pressure  (1)

[0072] As evident from the above equation, the flow rate of theorganosilane gas is limited by its partial pressure. The flow rate ofthe organosilane gas has a direct effect on the film deposition rate. Itis generally desirable to introduce as much of the organosilane aspossible in order to ensure a sufficiently high deposition rate. Aswould be known to those of skill in the art, the chemical supplier,e.g., a company such as Dow Corning, can provide a list of recommendedmaximum gas flows at various pressures for organosilane precursors(e.g., TMS) that they supply.

[0073] In some embodiments it is preferred that deposition pressure beset above about 50 Torr and below about 450 Torr. Higher pressuresgenerally increase the gas phase reactions of the ozone/organosilanereaction. It is desirable that the gas phase reactions result in a finalproduct (carbon-doped silicon oxide) being formed on the surface of thesubstrate. If the gas phase reaction is too strong (e.g., at a pressurelevel about 450 Torr), final product may be formed in the gas phaseabove the substrate surfaces rather than on the surface. Pressures above50 Torr are generally desirable to promote good heat transfer betweenthe substrate and pedestal and to achieve good gap fill performancecharacteristics.

[0074] The ozone flow rate also has a strong effect on deposition rate.Flowing more ozone into the chamber allows for more gas phase reactionsbetween the ozone and the organosilane thereby increasing the rate offilm deposition. Similarly, flowing a higher concentration of ozone, forexample, 16 wt. % as opposed to 8 wt. %, also results in an increase inthe deposition rate.

[0075] Preferred embodiments of the present invention also introduce aninert gas flow, in addition to the organosilane and ozone precursor gasflows, into the chamber during the deposition process. The inert gasflow helps stabilize the deposition process and improves the thicknessuniformity of the deposited film. Currently preferred embodimentsintroduce a flow of helium as the inert gas, but other embodiments canintroduce other gases such as argon or nitrogen. The inert gas shouldnot include elements that incorporate into the film in any significantmanner.

[0076]FIG. 7 is a graph showing the effect of an inert gas flow ofhelium on film uniformity. As evident by FIG. 7, the inventors havedetermined that a high flow of helium improves film uniformity, but oncethe flow reaches a certain rate, 6000 sccm for this particular set ofdeposition conditions, a further increase in the inert gas flow does notfurther improve film uniformity. The addition of a high flow of heliumdoes not adversely affect other film qualities such as deposition rateor refractive index.

[0077] Higher deposition pressure levels generally result in better gapfill properties but lower deposition rate and dielectric constants.Thus, it is important to balance these resulting characteristicsdepending on the desired physical properties of the deposited film. Inone set of experiments, in which the pedestal temperature was set to200° C., the heat temperature of a single exchanger coupled to both thelid and walls was set to 55° C., spacing was set to 210 mils and aprocess gas of TMS (170 sccm), helium (6000 sccm) and 12.5 wt. % ozone(4000 sccm) was introduced, pressure was set to 50 Torr and then to 200Torr. At 50 Torr the film had a deposition rate of 978 Å/min and a k of2.58. At 200 Torr the film had a deposition rate of 831 Å/min and a k of2.69. The gap fill properties of the 200 Torr film were improved ascompared to the 50 Torr film, however.

[0078] One experiment was performed in a chamber wherein separate heatexchangers were configured to maintain the walls at approximately 55° C.and the lid assembly at about 25° C. The other deposition conditionswere approximately the same as in the previous example, however the filmhad a deposition rate of approximately 1700 Å/min at a pressure of 100torr.

[0079] The present inventors have found that, subsequent to filmdeposition, a film cure step (FIG. 3, step 310) can improve filmstability, especially if the deposited film is subject to anenvironment, e.g., the clean room ambient, that contains moisture. Sucha cure process forces out moisture already absorbed into the film andchanges the film structure so that it is more moisture resistant. Thecure process removes undesirable Si—O “cage like” bonds and replacesthem with the more desirable Si—O “network” type bonds as would beunderstood by a person of skill in the art.

[0080]FIGS. 8A and 8B compare a cured carbon-doped silicon oxide filmwith uncured film. FIG. 8A shows Fourier transform infrared spectrometry(FTIR) data of an as deposited carbon-doped silicon oxide film depositedfrom TMS, ozone and helium precursor gas mixture. As shown in FIG. 8A,the film contains a relatively high number of Si—O cage-like bonds(wavenumber 1150 cm⁻¹) and very few of the desirable Si—O network typebonds. The cage-like bonds have dangling bonds and are susceptible toattracting hydrogen atoms in the presence of moisture such as moisturevapor. As shown in FIG. 8B, once the film is cured, however, many of theSi—O cage-like bonds are converted to the network type bonds resultingin a more stable, highly moisture resistant film. The film deposited forthe test shown in FIG. 8A also exhibited a strong stress hysteresis whenheated and subsequently cooled and a high dielectric constant (k=5.5)due to moisture absorption when exposed to the ambient for a one weekperiod. In contrast, the film deposited and cured for the test in FIG.8B, exhibited no stress hysteresis when heated and subsequently cooledand retained a low dielectric constant (k=2.5) even when exposed to theambient for a week.

[0081] Several different processes can be performed to effectively curefilms deposited according to the present invention. Two process thatshould not be used, however, include an oxygen plasma cure or a cure inan ozone rich furnace environment. Such processes can result in oxygenatoms reacting with the deposited film and removing the highly desirableSi—C bonds. When this happens the dielectric constant of the filmgreatly increases and the film becomes unsuitable for applicationsrequiring low dielectric constants.

[0082] Instead, the cure process can be performed in a conventionalfurnace with a relatively inert atmosphere, e.g., nitrogen, oxygen, orammonia, or under vacuum conditions. In either case, the cure can bedone in situ, i.e., without breaking vacuum, or ex situ, but ex situprocesses are generally preferred since in situ processes require use ofa relatively expensive deposition chamber and can significantly reducethroughput of the tool.

[0083] In either a conventional furnace or vacuum chamber, the cureprocess heats the film to a temperature between about 300-500° C. for atleast about 10 minutes. Higher temperature cures generally take lesstime than lower temperature ones. For example, a 300° C. cure may lastfor 40-60 minutes while a 500° C. cure may last for 10-20 minutes.

[0084] In a specific embodiment, a vacuum cure heats the substrate to atemperature of about 400° C. for a period of about 10 minutes in a lowpressure nitrogen environment. Such a process stabilizes the depositedfilm so that it resists moisture absorption in the future. The substratemay be transferred to another chamber, e.g. a different chamber in thesame cluster tool as the deposition chamber, for curing without breakingvacuum. A specific embodiment of a conventional furnace cure also heatsthe substrate to a temperature of about 400° C. for a period of about 30minutes in a nitrogen atmosphere.

[0085] Instead of placing the substrate in a vacuum environment,however, the substrate is placed in a molecular nitrogen (N₂)environment at atmospheric pressure. The furnace cure process ispreferred to a vacuum cure in some embodiments because it achievessimilar or even better film results with less expensive equipment andincreased throughput. Throughput is increased because wafers can betransferred into and out of the furnace, which can heat multiple wafersat a time, one at a time as they have finished the curing cycle, e.g.,30 minutes. While a vacuum chamber can also heat and cure multiplewafers at a time, the wafers are loaded and unloaded in batches so as tonot break vacuum while the curing process is underway.

[0086]FIG. 9 is a flowchart of one embodiment of a thermal depositionprocess, shown in FIG. 3 as step 305, that employs a process gas of TMS,ozone and helium. The process set forth in FIG. 9 is for exemplarypurposes only and should not be considered limiting to the scope of thepresent claims. The deposition process is initiated, after a wafer hasbeen loaded into the deposition chamber, by flowing helium (6000 sccm)and oxygen (4000 sccm) gases while keeping the throttle valve fully open(step 400) for several seconds in order to stabilize the gas flows.Oxygen (O₂) is added to the helium flow at the same rate at which ozoneis subsequently added. Flowing oxygen in this manner results in asubstantially constant oxygen/helium ratio throughout the depositionprocess. It is believed that maintaining such a constant ratio improvesfilm uniformity. An ozone flow is not introduced at this stage becausethe high reactivity of ozone.

[0087] Once the gas flow has stabilized, the throttle valve is partiallyclosed and the pressure within the chamber is brought to the desireddeposition pressure level in the presence of the helium and oxygen flows(step 405). Once the desired pressure level is reached and maintainedfor a couple of seconds, an ozone flow (4000 sccm) is substituted forthe oxygen flow and a flow of TMS is initiated (500 sccm) to deposit acarbon-doped silicon oxide film (step 410). Deposition step 410 ismaintained until the carbon-doped silicon oxide layer reaches a desiredthickness and then the ozone flow is shut off (step 415). The ozone flowis switched off prior to the TMS flow in order to allow the TMS to reactwith residual ozone in the gas phase. The present inventors havedetermined that shutting off the ozone and TMS flows simultaneously canresult in ozone reacting with carbon in the deposited film. The TMS flowis then shut off several seconds after the ozone flow (step 420) and thedeposition pressure is released by opening the throttle valve whilemaintaining the helium flow (step 425). Finally, all the gases are shutoff (step 430).

[0088] The pedestal and heat exchanger temperatures are set andstabilized prior to film deposition. All three temperatures aremaintained approximately constant throughout deposition. In the aboveexample, both the walls and lid of the deposition chamber weremaintained at a temperature of about 55° C. Generally these temperaturesare set and remain unchanged throughout an entire run of multiple waferdepositions.

[0089] In an alternative embodiment, the chamber walls are maintained ata temperature of about 60° C. and lid assembly is maintained at about25° C. In this embodiment the helium flow rate is 8000 sccm and theoxygen flow rate is 5000 sccm in step 400.

[0090] As described above, the present invention deposits a carbon-dopedsilicon oxide film that has good gap fill capabilities and a lowdielectric constant. The film is also highly conformal. Films depositedaccording to the present invention are porous when compared to thermalsilicon oxide. For example, thermal silicon oxide films generally have adensity of between 2.1-2.2 g/cm³. Films deposited according to thepresent invention, however, generally have a density of less than orequal to about 1.2 g/cm³.

[0091] The porosity of the film is provided by very small or microporesas opposed to larger pores found in some porous oxide films. Generally,these micropores are evenly distributed throughout the film and havediameters less than about 100 Å. The present inventors have demonstratedthat films deposited according to the present invention exhibit uniformremoval rates across the surface of an entire wafer when subject to aCMP step. This is especially important for damascene processes that areused for the fabrication of many integrated circuits today as thesurface of the film can become highly planarized after the CMP stepallowing for very fine patters to be focused on a subsequently depositedmetal layer film during a photolithography step. In one series of tests,films deposited according to the present invention exhibited CMP removalrates of 3687 Å/min. and 3087 Å/min. at a nonuniformity rate of 4 and 5percent, respectively, as measured at 49 points across the surface ofthe wafer as would be understood by a person of ordinary skill in theart. These test results compared favorably to removal of a thermal oxidefilm at a rate of 1100 Å/min at a nonuniformity rate of 3 percent.

[0092] The gas flow rates recited and described above are optimized fordeposition processes run in a Gigafill or D×Z chamber manufactured byApplied Materials and outfitted for 200 mm wafers. A person of ordinaryskill in the art will recognize that the rates at which variousprecursor gases in the process gas are introduced are in part chamberspecific and will vary if chambers of other design and/or volume areemployed.

[0093] In other embodiments of the present invention, one or moredopants may optionally be included with the organosilane and ozoneduring deposition of the low-k layer for both PMD and IMD applications.For example phosphorous (P) may be added using, e.g., phosphine (PH₃)during the deposition described above to getter alkali metals, e.g.,sodium (Na), thereby reducing metal contamination of the deposited film.Boron may be added, e.g. using diborane (B₂H₆). Boron tends to make thedeposited film flow easily but also diffuses easily. Diffusion of Boronfrom the Si—O—C layer into an underlying silicon substrate might beuseful for doping the silicon for making a device, such as a gatestructure. Alternatively, both boron (B) and phosphorous may be addedduring deposition to produce a film that has a reduced viscosity and canbe reflowed to achieve high aspect ratio gap-fill for PMD applications.

[0094] The inventors of the present invention have also discovered thatthe deposition rate and gap fill properties of Si—O—C films areoptimized under different conditions. For example, the deposition rateof Si—O—C films is optimized when deposited with organosilanes at lowpressure, i.e., about 150 torr or less and high temperature, i.e.,greater than about 150° C. Gap fill properties of Si—O—C films, e.g.,step coverage, are optimized when the film is deposited at relativelyhigh pressure, i.e., greater than about 200 torr, and low temperature,i.e., about 125° C. or less. The conditions that optimize gap fillgenerally produce low deposition rates. The conditions that optimizedeposition rate generally provide poor gap-fill. Since the conditionsthat optimize deposition rate and gap fill are contradictory to eachother, it is problematic to optimize both in a single step depositionprocess.

[0095] To overcome this, an alternative embodiment of the depositionmethod described above optimizes both gap fill and deposition rate bydividing the deposition into two steps. The first step is optimized forgap fill while the second step is optimized for deposition rate. Thefirst and second steps are performed with the gas mixtures and flowrates essentially as set forth above with respect to FIG. 9. In thefirst step, the throttle valve position is set to establish a pressureof between 200 and 700 torr, preferably about 200 torr while thepedestal is maintained at a temperature of about 125° C. In the secondstep helium is provided at 8000 sccm and 15% by weight of O₃ in O₂ isprovided at 5000 sccm. The pedestal temperature is raised to betweenabout 150 and 170° C. while the pressure is maintained at between 50 and150 torr, preferably about 100 torr.

[0096] In another version of this embodiment, the second step can be aPECVD process. For example, a Si—O—C type low-k film can be deposited byenergizing a process gas mixture of an organosilane with nitrous oxide(N₂O) or O₂ to form a deposition plasma. Suitable organosilanes includemethylsilane, dimethylsilane (DMS), trimethylsilane (TMS),tetramethylsilane (T4MS) and phenylmethylsilane among others. The PECVDSi—O—C layer is under a compressive stress. The thermal deposited Si—O—Clayer is under tensile stress. When the two layers are deposited on topof one another to form a combined film the compressive and tensilestresses tend to compensate for each other producing a low stress film.Such a low stress film would be resistant to cracking.

[0097] III. Process Integration of Deposition of a Low DielectricConstant Layer

[0098] While the above described ozone/organosilane carbon-doped siliconoxide film is useful for a variety of applications, the presentinventors have developed a number of pre-deposition and post-depositionsteps that facilitate the integration of a low K ozone/organosilanecarbon-doped silicon oxide film according to the present invention intoestablished integrated circuit manufacturing processes. One example ofsuch a multistep process is depicted in FIG. 10. As shown in FIG. 10,the process starts with a pre-deposition treatment 1000 to enhance theadhesion of the film to underlying aluminum. The pre-depositiontreatment 1000 uses free atomic hydrogen to reduce an aluminum oxidethat builds up on the aluminum. In a specific embodiment, free atomichydrogen is dissociated from a hydrogen-containing gas in a remotesource. In another specific embodiment, the remote source energizes thehydrogen containing gas with electromagnetic radiation. In a preferredembodiment the electromagnetic radiation is in the form of microwaves.Further details of predisposition step 1000 are described below inconjunction with FIGS. 11a and 11 b.

[0099] After pretreatment step 1000, layer of carbon-doped silicon oxideis deposited in step 1010 using an organosilane and ozone. This step haselements in common with the method set forth above with respect to FIG.3 and FIG. 9.

[0100] An optional post deposition treatment 1020 further enhancesadhesion by reducing shrinkage of the deposited film. This step isgenerally performed if the film is to be cured ex-situ. Thepost-deposition treatment 1020 takes place in a reducing environment. Ina preferred embodiment, the deposited film is treated in a reducingenvironment of ammonia for approximately one minute at a temperature ofapproximately 400° C.

[0101] The method then proceeds to a cure 1030(step 310 from FIG. 3),which may be performed either in-situ or ex-situ. After cure 1030, thefilm can be densified at 1040 to reduce outgassing of a subsequentlydeposited cap layer. In a preferred embodiment, the cured film isdensified in a nitrogen-containing plasma. After densification 1040, thefilm can be capped at 1050 to prevent cracking of the film. In oneembodiment, a cap layer of silicon oxide is deposited over the densifiedfilm by plasma enhanced chemical vapor deposition (PECVD). Furtherdetails of steps 1020, 1040 and 1050 are set forth in Section V, VI andVII below.

[0102] IV. Pre-Deposition Treatment

[0103] Predeposition step 1000 discussed in FIG. 10 provides for strongadhesion of a layer of material deposited on an underlying substrate.For example, in some IMD applications a dielectric layer, such as aTMS-ozone layer, may adhere poorly to an underlying metal. Postdeposition heating processes, such as cure processes, may cause thedeposited film to shrink. As a result of the shrinkage, the depositedlayer can become delaminated from the underlying metal. The adhesionproblem is illustrated in FIG. 11a, which depicts a partially formedintegrated circuit 1100. Integrated circuit 1100 generally includes anoxide layer 1102 and metal lines 1104 separated by a gap 1106. An uppersurface 1105 of metal lines 1104 may be coated with a thin barrier suchas titanium nitride (TiN). In the case of aluminum metal lines 1104,poor adhesion is believed to the result of a thin layer 1110 of aluminumoxide (Al_(x)O_(y)) on the surface of vertical walls 1112 of metal lines1104. If oxide forming layer 1110 is one that forms readily at roomtemperature, layer 1110 tends to be weakly bonded to the underlyingmetal, i.e. metal lines 1104. Consequently a film deposited over oxide1110 may become delaminated from metal lines 1104.

[0104] Previously known methods used to remove such an oxide layerinclude sputtering in a plasma. Ions from the plasma are acceleratedtowards the circuit 1100 in the direction shown by arrows 1114 by anelectric field. Sputtering is effective at removing oxide from a bottomof gap 1106. Unfortunately because of the direction of acceleration ofthe ions, the plasma is much less effective at removing the oxide fromthe walls 1112.

[0105] To overcome this, one embodiment of the present inventionincludes a pre-treatment step in which the oxide layer is reduced withfree atomic hydrogen. The pre-treatment is illustrated in FIG. 11b. Freeatomic hydrogen 1120 attacks the oxide in a purely thermal reaction inall directions as shown by arrows 1122. Since the thermal reaction isnon-directional hydrogen 1122 can attack oxide 1110 on vertical walls1112. Such a pretreatment can effectively remove aluminum oxide and mayalso be effective in reducing other metal oxides such as copper oxides(Cu_(x)O_(y)). Furthermore, such a pre-treatment is generallyadvantageous when a surface of a substrate contains a weakly bound oxidethat would impair adhesion of a subsequently deposited layer ofmaterial.

[0106] As shown in FIG. 2, a remote source, fluidly coupled to theprocess chamber provides free atomic hydrogen for the pre-treatment. Theremote source supplies energy that dissociates a hydrogen-containing gassuch as ammonia (NH₃) or molecular hydrogen (H₂). Such a remote sourcecan be a purely thermal source, in which hydrogen containing gas isdissociated by heating at a high temperature. More preferably, theremote source is a remote plasma source that dissociateshydrogen-containing gas in a plasma that is initiated and sustained withenergy in the form of electromagnetic radiation. In this application,electromagnetic radiation is taken to mean any form of radiationresulting from oscillating electromagnetic fields. Such radiationincludes but is not limited to all bands of the electromagnetic spectrumincluding long wave, radiofrequency, microwave, infrared, visibleultraviolet, x-ray and gamma ray. Still more preferably, the remotesource dissociates hydrogen-containing gas with radiation having afrequency of between about 100 kilohertz (kHz) and 100 gigahertz (GHz).A strike gas such as argon (Ar) or nitrogen (N₂) may optionally besupplied to the remote plasma source to facilitate striking the plasma.

[0107] Two examples of such remote sources are shown in FIGS. 12a and 12b. The deposition chamber 15 generally includes a remote clean source202 for cleaning the chamber with nitrogen trifluoride (NF₃), as shownin FIG. 2. Such a remote clean sources can be coupled to the systemcontroller and configured to operate in response to instructionsembodied in a computer program. This same remote clean source 202 can beconfigured to selectively receive a hydrogen-containing gas for thepre-treatment described above.

[0108]FIG. 12a depicts a remote RF plasma source 1200. Remote RF plasmasource 1200 generally comprises a remote chamber 1202 coupled to gassources 1204 via gas lines 1205. Remote chamber 1202 is fluidly coupledby a conduit 1207 to a process chamber such as chamber 15 depicted inFIGS. 1a and 1 b. Gas sources 1204 provide hydrogen-containing gas toremote chamber 1202. Remote chamber 1202 includes gas deflectors 1206and an RF electrode 1208. Deflectors 1206 direct the flow of gas in aspiral flow pattern 1212 within remote chamber 1202. RF electrode 1208is coupled to an RF generator 1210. RF generator 1210 delivers energy inthe form of RF radiation to the hydrogen containing gas via RF electrode1208 Spiral pattern 1212 increases the residence time ofhydrogen-containing gas in remote chamber 1202 thereby facilitatingdissociation of free atomic hydrogen from the hydrogen containing gas.In one embodiment RF generator 1210 provides between 2000 and 5000 wattsof RF power, preferably 3000 watts at frequency of between 1 MHz and 100MHz, preferably about 13.56 MHz. NH₃ is provided to remote RF plasmasource 1200 at about 950 sccm. Argon is also provided to remote RFplasma source 1200 at about 1500 sccm. An example of a suitable remoteRF source 1200 is an ASTRON™ manufactured by Applied Science andTechnology (ASTeX), of Woburn Mass. Such a source is capable ofdissociating NH₃ with an efficiency of 95%.

[0109]FIG. 12b depicts a remote microwave plasma source 1250. Remotemicrowave plasma source 1250 generally comprises a microwave transparentdischarge tube 1252 coupled to gas sources 1254 via gas lines 1255.Discharge tube 1252 is typically made from a dielectric material such asquartz. Discharge tube 1252 is fluidly coupled by a conduit 1253 to aprocess chamber such as chamber 15 depicted in FIGS. 1a and 1 b. Gassources 1254 provide hydrogen-containing gas to discharge tube 1256.Discharge tube 1252 is situated within a tunable microwave cavity 1256.Microwave cavity 1256 is coupled to a microwave generator 1258 via amicrowave transmission-line or waveguide 1260. Microwave cavity 1256generally includes fixed walls 1257 a and a movable wall 1257 b. Movablewall 1257 b moves longitudinally with respect to fixed walls 1257 athereby tuning cavity 1256 to optimize transfer of microwave power tothe hydrogen containing gas. In one embodiment the microwave generatorprovides between 1500 and 2500 watts, preferably about 2100 watts ofmicrowave power at frequency of between 1 and 5 GHz, preferably about2.2 GHz. An example of a suitable remote microwave source 1250 is aRemote Clean™ source manufactured by Applied Science and Technology(ASTeX), of Woburn Mass. Such a source is capable of dissociating NH₃with an efficiency of 99%.

[0110] In a preferred embodiment of the pre-treatment process, theremote microwave source operates at a frequency approximately 2.2gigahertz and a power of 2100 Watts. NH₃ is provided to remote themicrowave source at 950 sccm. The substrate is generally at atemperature of 100° C. to 400° C. and the chamber wall is typically at atemperature of 65° C. The pressure in the remote source is approximately8 torr and the chamber pressure is approximately 5 torr.

[0111] While the present invention is initially developed pretreatmentstep 1000 in the context of an organosilane/ozone carbon-doped siliconoxide film, pretreatment step 1000 is applicable to any type of filmthat would benefit from atomic hydrogen treatment of the underlyinglayer.

[0112] V. Post Deposition Treatment

[0113] After deposition, a silicon carbon or Si—O—C film is often quiteporous. Consequently, the film tends to absorb moisture. The absorbedmoisture generally degrades the properties of the film. In the case of alow-k film, moisture tends to increase the dielectric constant of thefilm and is detrimental to film adhesion. The porosity is normallyreduced during the previously described thermal cure. However, if thecure is performed ex-situ, the film is exposed for a time to moisturefrom the ambient atmosphere (e.g., the clean room atmosphere). The filmmay also tend to shrink during subsequent polymerization and curingprocesses.

[0114] Additional modifications to the above described depositionprocess provide for a post deposition treatment to enhance adhesion of alow-k dielectric layer to a subsequently deposited layer and reduceshrinkage. The post-deposition treatment (step 1020 in FIG. 10)generally includes a densification step performed before removing thesubstrate from vacuum. The densification involves heating the substratein a reducing ambient atmosphere to reduce shrinkage of the low-kdielectric layer. Suitable reducing environments include NH₃ and H₂. Thedensification can be performed in the same chamber as the deposition, ora different chamber. If done in a different chamber, however, the waferis preferably transferred to that chamber under vacuum controlledconditions.

[0115] In one embodiment of the post-deposition treatment the substrateis heated in an NH₃ ambient to between approximately 300 and 500° C.,preferably about 400° C. for between 1 and 5 minutes, preferably about1.5 minutes, at a pressure below atmospheric pressure. If the pressurein the chamber is above atmospheric pressure there is a possibility thegreater pressure might cause the chamber lid to open. Typically, thepressure is between about 200 and 700 torr, preferably about 600 torr.

[0116] The densification described above is not normally employed inembodiments where the substrate is cured without breaking vacuum afterdepositing the low-k film. While the present inventors have found postdeposition step 1020 to be particularly useful to stabilize low kozone/organosilance carbon-doped silicon oxide films deposited accordingto the present invention and that are subsequently cured in an ex-situprocess, step 1020 is a useful treatment for any film that is unstablein air. Such a densification is particularly useful for protecting lowtemperature deposited films that undergo an ex-situ cure. Such filmsinclude TMS-ozone films, spin on glass (SOG) and Black Diamond™. In thecase of Black Diamond™, the densification is performed in an oxygen (O₂)ambient to remove hydrogen from the film.

[0117] VI. Post-Cure Plasma Densification treatment

[0118] Si—O—C low-k films that have been deposited in accordance withthe pre-deposition, deposition, post deposition, and curing processesdescribed above are often subject to oxidizing environments in thecourse of subsequent processing. Such oxidizing processes include, butare not limited to, etching, photoresist strip and oxide cappingprocesses. The low-k film is typically a silicon-oxy-carbon structure.In an oxidizing environment the low-k film can react with oxygen andhydrogen to form carbon dioxide (CO₂) and water vapor (H₂O). Thereaction removes carbon from the film leading to shrinkage and increasein k-value.

[0119] The situation is illustrated in the Fourier transform infrared(FTIR) spectra depicted in FIGS. 13a-13 d. FIG. 13a depicts a first FTIRspectra 1302 for an as-deposited Si—O—C low-k film. Note the presence ofC—H and Si—C bonds in the spectra indicating the desired Si—O—Cstructure. To simulate the effect of an oxidizing environment duringprocessing, the as deposited film was subjected to an oxygen plasma for3 minutes at 400° C. The oxygen plasma produces active oxygen speciesthat attack the film. A second FTIR spectra 1304 taken after oxygenplasma treatment shows little or no C—H and Si—C bonds indicating theremoval of carbon from the film. The FTIR spectra in FIG. 13b. show thatoxygen plasma also removes carbon from a post-cured Si—O—C film. Spectra1306, for example, was taken on a post cured TMS-ozone deposited film.Spectra 1308 was taken on the same film after treatment in oxygen plasmafor 3 minutes at 400° C.

[0120]FIG. 13c depicts FTIR spectra from a similar experiment in whichthe as-deposited film was subjected to baking in an O₃ environment at400° C. As in FIG. 13a, a post deposition FTIR spectrum 1310 shows C—Hand Si—C bonds while a post bake FTIR spectra 1312 does not. The O₃ bakeremoves carbon from the film, which is believed to cause a collapse ofthe film structure resulting in a shrinkage in film thickness. Thepost-O₃-bake film also exhibited increased refractive index and moistureabsorption. Furthermore, a post-cured film exhibited the same behavioras shown in post-cure spectra 1314 and post-bake spectra 1316 of FIG.13d.

[0121] In addition to degradation of the cured film's properties, thefilm tends to outgas during subsequent heating (e.g., during annealing).The outgassing can cause bubbles that lead to delamination of asubsequently deposited layer.

[0122] To overcome these problems, another embodiment of the method ofthe present invention includes a densification treatment after the filmis cured. The densification process is an optional process that depends,to a certain extent, on the type of low-k film. For example, adensification step is not normally implemented for a barrier low-k(BLOK™) film since this type of film has a silicon carbide (Si—C)structure that is not normally subject to oxidation. The plasmadensification process is particularly useful for Si—O—C films depositedusing an organosilane. Typically the densification plasma is an RFplasma containing helium (He), nitrogen (N₂), or Argon (Ar).Alternatively an RF or remote microwave plasma containing NH₃ and O₂ maybe used. Preferably, the plasma is formed from a gaseous mixture of Heand N₂. Ar plasma is not normally if sputtering would be a problem.However, Ar plasma may be used if, for example, sputtering is a desiredeffect.

[0123] In one embodiment, a substrate containing a TMS-ozone depositedlow-k film is cured in-situ at approximately 400° C. for betweenapproximately 3 and 30 minutes, preferably about 10 minutes. The curedfilm is then subjected to N₂ plasma for approximately two minutes whilethe substrate is heated to between approximately 350 and 450° C.,preferably about 400° C. The chamber pressure is typically maintained atbetween about 1.2 and 5.0 torr, preferably about 1.5 torr. The plasma issustained by radiofrequency (RF) energy delivered at a power of between500 and 900 watts, preferably about 700 Watts and a frequency of between100 KHz and 100 MHz, preferably about 450 KHz. One example of a suitablechamber for the densification process is a D×Z PECVD chambermanufactured by Applied Materials of Santa Clara, Calif. Such a chamberis described in U.S. Pat. No. 5,558,717.

[0124]FIG. 13e depicts FTIR spectra taken for TMS/ozone deposited Si—O—Cfilm that was treated with the densification described above following apost-deposition cure. Spectra 1318, taken for the as-deposited film,exhibits the C—H and Si—C bonds characteristic of the desired filmstructure. The as-deposited film was cured and then subjected todensification in an N₂ plasma. In this case, the substrate temperaturewas 250° C., and chamber pressure was 4.5 torr during plasmadensification. Nitrogen was provided at a flow rate of 2000 sccm. RFpower of 700 watts was provided at a frequency of 13.56 MHz. Spectra1320 was taken on the same film after the N₂ plasma treatment. Note thatthe C—H and Si—C bonds are little changed compared to as-depositedspectra 1318. The densified film was then subjected to a first oxygenplasma for 3 minutes at a substrate temperature of 250° C. Spectra 1322,taken after the first oxygen plasma treatment, shows little change inthe C—H and Si—CH₃ bonds. The same film was then subjected to a secondoxygen plasma for 3 minutes at a substrate temperature of 400° C.Spectra 1224, taken after the second oxygen plasma treatment, againshows little change in the C—H and Si—CH₃ bonds. Table I shows theeffect of the N₂ and oxygen plasma treatments on film properties. TABLEI Shrinkage after Refractive Film Thickness (Å) initial cure (%) IndexAs-deposited 3716.2 1.428 Post-cure 3440.3 1.397 N₂ plasma treated3394.3 1.34 1.397 250° C. O₂ plasma 3287.4 4.44 1.396 400° C. O₂ plasma3249.3 5.55 1.396

[0125] As can be seen in FIG. 12e, the plasma densification processstabilizes the film and prevents removal of carbon in an oxidizingenvironment such as etch and photoresist strip. Table I demonstratesthat the N₂ treatment has a negligible effect on the refractive index(and therefore k-value) of the film. Table I further demonstrates thatthe N₂ densification process produces relatively little shrinkage of thepost cured film.

[0126] Furthermore, the present inventors have discovered that if anoverlying cap layer is deposited over an ozone/organosilane filmaccording to the present invention, densification treatment 1040prevents delamination of an overlying cap layer due to bubble formation.Bubbles may form with an undensified Si—O—C layer due to outgassing fromthe Si—O—C layer during high temperature processes such as annealing. Inan experiment, a low-k film was deposited on a substrate using TMS-ozoneas described above. After deposition, the substrate was cured for 5minutes at 400° C. After curing, the substrate was subject to N₂ plasmafor 2 minutes and then capped with PE TEOS. The substrate exhibited nobubbling of the cap layer even after annealing at 450° C.

[0127] VII. Capping TMS-ozone Deposited Layers

[0128] In some instances, the present inventors have found that Si—O—Cfilms that have been deposited in accordance with the pre-deposition,deposition, and post deposition and densification described above maystill be susceptible to cracking after curing as described above. Thisoccurs in spite of the fact that the observed stress, the k-value, andthe FTIR spectrum for the film do not change over time. The presentinventors have observed that the susceptibility of the film to crackingdepends upon the thickness of the deposited film and the length of timeto which the film is exposed to the ambient (air). A post-cured film6000 Å or less in thickness, that has not undergone plasmadensification, is typically stable, i.e. it does not crack after anindefinite period of time after exposure to ambient. At 8000 Å anundensified film cracks after about one week exposure. At 1.2 microns,and undensified film typically cracks upon removal from the chamber,i.e., upon exposure. Generally, the thicker the film, the sooner thefilm cracks. Densification also affects the thickness at which the filmcracks. For example, the present inventors have found that a post curedorganosilane deposited Si—O—C film that has not been densified in anitrogen plasma, as described above, cracks at thickness of 8000 Å ormore within about a week. A comparable film, that has undergone plasmadensification, is stable up to a thickness of about 1.2 microns. Atabout 1.6 microns thick, a plasma densified film cracks after about twodays. At 2 microns thickness, or greater, a densified film typicallycracks upon removal from the chamber.

[0129] To overcome this, another embodiment of the present inventionincludes capping the TMS-ozone deposited low-k film with a layer ofoxide or nitride. It is believed that the if the cap layer is harderthan TMS-ozone low-k layer the cap layer physically holds the low-k filmtogether. The cap layer provides a barrier against moisture penetrationof the low-k film. The cap layer, typically a silicon oxide or siliconnitride, may be deposited by any conventional means. Preferably the caplayer is a silicon oxide deposited to a thickness of between 1000 Å and3000 Å by plasma enhanced chemical vapor deposition (PECVD) using aprecursor such as TEOS. Such a cap layer is refered to herein as a PETEOS layer. The inventors have found that a TMS-ozone film that has beenplasma densified and capped with a 1000 Å PE TEOS film is stable up to athickness of 1.6 microns. At about 2 microns thick, a densified andcupped film cracks after 3-4 days. Silicon nitride generally provides astronger cap layer and a better moisture barrier. Consequently, siliconnitride cap layers can be thinner, perhaps for example, or the order ofa few hundred angstroms.

[0130] In some applications, a cap layer might be undesirable. Forexample in processes that require a low interlayer capacitance, such asdamascene processes, a cap layer might not be used. The inventors havefound however that capping solves the problem of film cracking.

[0131] VIII. Exemplary Enhanced Deposition of an Si—O—C Layer

[0132]FIGS. 14a-14 f depict detailed flow diagrams of the steps of anexemplary embodiment of the method of the present invention depicted inFIG. 10. In this exemplary embodiment, the substrate is pre-treatedusing a remote microwave plasma containing NH₃ in step 1000. The Si—O—Clayer is deposited with TMS-ozone using dual heat exchangers in step1010. The as-deposited Si—O—C layer is densified in a reducing ambientof NH₃ in step 1020 and furnace cured ex-situ in step 1030. In analternative embodiment, the Si—O—C film is cured in-situ anddensification step 1020 is omitted. The cured Si—O—C layer is densifiedin a nitrogen containing plasma in step 1040 and capped with PE TEOS instep 1050.

[0133] The flow diagram of FIG. 14a shows the details of an exemplarypretreatment step, shown in FIG. 10 as step 1000. In the pre-treatmentprocess of FIG. 14a. A wafer is inserted into the chamber at step 1401.Gas flows and temperatures are established in step 1402. NH₃ is suppliedto the remote microwave source at about 950 sccm. The pressure isstabilized at about 8 torr in the microwave source and 8 torr in thechamber. The pedestal is maintained at a temperature of approximately125° C. and the chamber wall is typically at a temperature ofapproximately 65° C. during pretreatment. In step 1403, the remotemicrowave source applies microwaves to the gases to ignite the remoteplasma. The microwave frequency is approximately 2.2 gigahertz andmicrowave power is about 2100 Watts. In step 1404, atomic hydrogenproduced in the plasma treats the substrate for between about 1 to 5minutes, preferably about 1.5 minutes. Finally, the gases and microwavesare shut off (step 1405).

[0134]FIG. 14b is a flowchart of one embodiment of a thermal depositionprocess, shown in FIG. 10 as step 1010, that employs a process gas ofTMS, ozone and helium. This particular embodiment utilizes dual heatexchangers to separately control chamber wall temperature and chamberlid temperature. The process set forth in FIG. 14b is for exemplarypurposes only and should not be considered limiting to the scope of thepresent claims. The pedestal and heat exchanger temperatures are set andstabilized prior to film deposition in step 1411. All three temperaturesare maintained approximately constant throughout deposition. In theabove example, the walls are maintained at about 60° C., the lid of thedeposition chamber is maintained at a temperature of about 25° C. andthe pedestal is maintained at a temperature of about 400° C. Thedeposition process is initiated, after a wafer has been loaded into thedeposition chamber, by flowing helium (8000 sccm) and oxygen (5000 sccm)gases while keeping the throttle valve fully open (step 1412) forseveral seconds to stabilize the gas flows. Ozone is not introduced atthis stage because the high reactivity of ozone.

[0135] Once the gas flow has stabilized, the throttle valve is partiallyclosed and the pressure within the chamber is brought to the desireddeposition pressure level in the presence of the helium and oxygen flows(step 1413). Once the desired pressure level is reached and maintainedfor a couple of seconds, an ozone flow (5000 sccm) is substituted forthe oxygen flow and a flow of TMS is initiated (500 sccm) to deposit acarbon-doped silicon oxide film (step 1414). Deposition step 1414continues until the carbon-doped silicon oxide layer reaches a desiredthickness and then the ozone flow is shut off (step 1415). The ozoneflow is switched off prior to the TMS flow in order to allow the TMS toreact with residual ozone in the gas phase. The TMS flow is then shutoff several seconds after the ozone flow (step 1416) and the depositionpressure is released by opening the throttle valve while maintaining thehelium flow (step 1417). Finally, all the gases are shut off (step1418).

[0136] The flow diagram of FIG. 14c shows the details of an exemplarypost-deposition densification step, shown in FIG. 10 as step 1020. Inthe exemplary embodiment, this step is performed because the substrateis cured ex-situ in the following step. The exemplary post-depositiondensification begins at step 1421, by establishing gas flows andtemperatures. NH₃ is supplied at a pressure of about 600 torr and thesubstrate is heated to about 400° C. The substrate is treated for about90 seconds minutes in step 1422. Gases pedestal heating are shut off andthe pedestal allowed to cool in step 1423.

[0137] The flow diagram of FIG. 14d shows the details of an exemplaryfurnace cure, shown in FIG. 10 as step 1030. In the exemplaryembodiment, the substrate is removed from a vacuum environment andplaced in a furnace in step 1431. Of course, multiple wafers may beplaced in the furnace for simultaneous curing. Substrate processthroughput is generally optimized when as many substrates as possibleare furnace cured at the same time. An ambient atmosphere of nitrogen(N₂) is provided to the furnace at step 1432. The furnace then heats thesubstrate to a temperature of about 400° C. for a period of about 30minutes in step 1433.

[0138] The flow diagram of FIG. 14e shows the details of an exemplaryin-situ cure, shown in FIG. 10 as step 1030. Such a cure can beperformed in a chamber such as that depicted in FIGS. 1A-1F. Thepedestal temperature and gas flows of helium He and O₂ are establishedwith the throttle valve open in step 1434. He is supplied at about 6000sccm and O₂ is supplied at about 3000 sccm. The pedestal temperature isset to about 400° C. The presence of O₂ enhances shrinkage during thecure. In step 1435, the throttle valve is partially closed to raise thepressure in the chamber to about 450 torr. The substrate is then heatedwith the pedestal at a temperature of 400° C. and the chamber pressureat 450 torr for about 10 minutes in step 1436. The flow of oxygen isshut off at step 1437 and the chamber is purged. The pressure is raisedto about 800 torr by further closing the throttle valve. In step 1438,the throttle valve is fully opened. The helium flow is reduced to about2000 sccm and a flow of about 500 sccm of N₂ is introduced to thechamber.

[0139] The flow diagram of FIG. 14f shows the details of an exemplarypost-cure plasma densification step, shown in FIG. 10 as step 1040. Theplasma densification may be performed in a processing chamber of thetype depicted in FIGS. 1A-1F. If the cure step preceding the plasmadensification was an in-situ cure, plasma densification may take placein the same chamber as the cure. If the cure step was a furnace cure,the post cured substrate is removed from the furnace and placed in aprocessing chamber in step 1441. A process gas of N₂ is supplied to thechamber in step 1442. The process gas is then ignited to form a plasmain step 1443. The substrate is then subjected to N₂ plasma forapproximately two minutes while the substrate is heated to about 400° C.in step 1444. The chamber pressure is maintained at about 1.5 torr. Theplasma is sustained by radio frequency (RF) energy delivered at a powerof about 700 Watts and a frequency of about 450 kHz. The RF power isturned off and the gas flows are stopped in step 1445.

[0140] The flow diagram of FIG. 14g shows the details of an exemplarycapping step, shown in FIG. 10 as step 1050. In the exemplaryembodiment, the cap layer is deposited on the plasma densified Si—O—Clayer in the same chamber as that used in the plasma densification step.Alternatively, the substrate containing the Si—O—C film may betransferred to a different chamber for capping. In step 1451, processgas flows and other process conditions are established. Helium isprovided at about 1000 sccm. TEOS is provided at about 1050milligrams/minute (mgm). Oxygen (O₂) is provided at about 1000 sccm. Thechamber pressure is generally about 8.2 torr and the pedestaltemperature about 400° C. In step 1452 the process gases are energizedto form a plasma. 1000 Watts of RF power are supplied at a frequency ofabout 13.56 MHz. In step 1453 a silicon oxide cap layer is depositedusing the plasma. Deposition proceeds until the cap layer has athickness of about 2000 Å. In step 1454, RF power is turned off and theflow of process gases is stopped. The substrate may then be removed fromthe chamber for further processing, such as photoresist deposition,metal deposition, etc.

[0141] The methods described above can be readily incorporated intoexisting process recipes. For example, FIGS. 15a-15 h depict one exampleof an IMD gap fill process incorporating the above method. In FIG. 15a afirst metal layer 1502 of A1 is deposited on an Si substrate 1500. Ananti-reflective coating of TiN 1504 is deposited on A1 layer 1502. InFIG. 15b a first photoresist layer 1506 is deposited on the TiN 1504.The walls of gaps 1508 are treated with free atomic hydrogen asdescribed above to reduce aluminum oxide. In FIG. 15c TiN and A1 layersare etched to form gaps 1508 using the patterned photoresist 1506. InFIG. 15d A low-k TMS layer 1510 is deposited, cured and densified asdescribed above to fill gaps 1508. TMS layer 1510 is capped with PE TEOS1512. PE TEOS layer 1512 is planarized (e.g., using CMP) and coveredwith a second patterned photoresist 1514 in FIG. 15e. PE TEOS and TMSlayers are then etched through second patterned photoresist layer 1514down to TiN layer 1504 to form vias 1516 as shown in FIG. 15f. Afteretching, photoresist 1514 is stripped, e.g., by ashing in an oxidizingenvironment. Densification treatment 1040 protects PE TEOS and TMSlayers during etch and photoresist strip. Vias 1516 are filled with ametal such as tungsten to form interconnects 1518 as shown in FIG. 15g.After planarization, a second metal layer 1520 and barrier layer 1522can be deposited over interconnects 1518 as shown in FIG. 15h. Theprocess of FIGS. 15b-15 h can then be repeated multiple times until thedesired integrated circuit structure is complete. Such a processintegration scheme is simple and involves relatively little complexitywith CMP, etch, and photoresist strip. Such a process does producerelatively high k values between the metal layers due to PE TEOS layer1512. Lower k values between the lines can be achieved, for example byeliminating the deposition of PE TEOS cap layer 1512.

[0142] A dual-damascene process integration scheme that utilizes thelow-k TMS-ozone deposition method described herein is depicted in FIGS.16a-16 h. The dual damascene process begins with the deposition of anoxide layer 1602 over a silicon substrate 1600 as shown in FIG. 16a. Ahardmask layer 1604, e.g., silicon nitride (Si₃N₄), is deposited overoxide layer 1602. A first low-k TMS layer 1606 is deposited, cured anddensified as described above. First TMS layer 1606 is covered with apatterned photoresist layer 1608 during a first photolithography asshown in FIG. 16b. In FIG. 16c, a first etch forms a first set of gaps1610 in first TMS layer 1606 down to hardmask layer 1604. After thefirst etch, photoresist 1608 is stripped, e.g., by ashing in anoxidizing environment. Densification treatment 1040 protects TMS layer1606 during etch and photoresist strip. Gaps 1610 and first TMS layer1606 are then covered with a layer of metal, such as aluminum or copper.In the case of copper, a seed layer 1612 (FIG. 16c) is deposited overgaps 1610 and first TMS layer 1606. A first bulk copper layer 1614 isdeposited to fill the gaps 1610 as shown in FIG. 16d. Copper layer 1614is planarized, e.g., by CMP. Copper layer 1614 forms, e.g., a first setof metal lines in an interconnect structure.

[0143] After planarization, of copper 1614, a second hardrnask layer1616, a second TMS 1618 layer, a third hardmask layer 1620 and third TMSlayer 1622 are deposited as shown in FIG. 16e. A second lithography andetch forms vias 1624 through layers 1616, 1618, 1620 and 1622 down tocopper layer 1614 as shown in FIG. 16f. In FIG. 16g, a third lithographyand etch forms a second set of gaps 1626. Gaps 1626 define a second setof metal lines and vias 1624 define a set of interconnects between thesecond set of metal lines and the first set of metal lines defined bygaps 1610 and copper layer 1614. Vias 1624 and gaps 1626 are then filledwith a second bulk copper layer 1628 as shown in FIG. 16h. The resultingstructure is then annealed and planarized.

[0144] Damascene processes are used in devices that use copperinterconnects because there is currently no acceptable way to etchcopper. Structures formed by damascene processes do not require agap-fill dielectric and generally provide lower RC delays than similarstructures formed using aluminum metal lines. Furthermore, higherdeposition rates may be used in damascene processes since gap-fill isnot an issue.

[0145] Having fully described several embodiments of the presentinvention, many other equivalent or alternative methods of depositingthe low dielectric constant oxide layer according to the presentinvention will be apparent to those skilled in the art. Thesealternatives and equivalents are intended to be included within thescope of the present invention.

What is claimed is:
 1. Apparatus for depositing thin films, comprising:a housing defining a process chamber having one or more walls and a lid;a first heat exchanger coupled to said walls; and a second heatexchanger coupled to said lid; wherein said first and second heatexchangers are configured to maintain said lid at a differenttemperature than said walls.
 2. The apparatus of claim 1, wherein atleast one of said one or more walls includes one or more heat exchangepassages coupled to said first heat exchanger.
 3. The apparatus of claim1 wherein said lid includes one or more heat exchange passages coupledto said second heat exchanger.
 4. The apparatus of claim 1, furthercomprising: a gas delivery system configured to introduce gases intosaid process chamber.
 5. The apparatus of claim 4, wherein said gasdistribution system includes: a gas distribution manifold attached tosaid lid.
 6. The apparatus of claim 5 wherein said gas distributionsystem further includes a gas distribution face plate fluidly coupled tosaid gas distribution manifold.
 7. The apparatus of claim 6 wherein saidgas distribution system further includes a blocker plate disposedbetween said manifold and said faceplate.
 8. The apparatus of claim 7wherein said second heat exchanger is configured to maintain said lid ata temperature such that a process gas does not react behind said blockerplate.
 9. The apparatus of claim 1, further comprising a substrateholder, adapted to hold a substrate during substrate processing.
 10. Theapparatus of claim 9, further comprising a heater, operatively coupledto heat said substrate holder.
 11. A substrate processing apparatus,comprising: a housing defining a process chamber having a substrateprocessing region, a first wall perimetrically surrounding saidsubstrate processing region, and a second wall positioned over saidsubstrate processing region, said first wall comprising a first fluidpassage within an interior of said first wall, said second wallcomprising a second fluid passage within an interior of said secondwall, wherein said first and second passages are not fluidly coupled toeach other; a first heat exchanger operatively coupled to maintain fluidwithin said first fluid passage at a first temperature; and a secondheat exchanger operatively coupled to maintain fluid within said secondfluid passage at a second temperature.
 12. The apparatus of claim 1,wherein said second wall is a chamber lid.
 13. A substrate processingsystem comprising: a housing defining a process chamber having one ormore walls and a lid; a substrate holder, adapted to hold a substrateduring substrate processing; a heater, operatively coupled to heat saidsubstrate holder; a gas delivery system configured to introduce gasesinto said process chamber; a first heat exchanger coupled to said walls;a second heat exchanger coupled to said lid; wherein said first andsecond heat exchangers are configured to maintain said lid at adifferent temperature than said walls; a controller for controlling saidgas delivery system and said heater; and a memory coupled to saidcontroller comprising a computer-readable medium having acomputer-readable program embodied therein for directing operation ofsaid controller, said computer-readable program including a first set ofinstructions to control said first heat exchanger to maintain said wallsat a first temperature; a second set of instructions to control saidsecond heat exchanger to maintain said second heat exchanger at a secondtemperature different from said first temperature; and a third set ofinstructions to control said gas delivery system to flow a process gascomprising ozone and an organosilane having at least one silicon-carbonbond into the substrate processing chamber and control said heater toheat the substrate holder to a temperature of between 100-250° C.
 14. Amethod for forming an insulation layer over a substrate disposed in asubstrate processing chamber having one or more walls and a lid, themethod comprising: flowing a process gas comprising ozone and anorganosilane through said lid into the substrate processing chamber;heating the substrate to a temperature of less than about 250° C. toform a carbon-doped silicon oxide layer over the substrate; maintainingthe walls at a first temperature; and maintaining the lid at a secondtemperature.
 15. The method of claim 14 wherein said first temperatureis chosen to optimize a reaction in said process chamber that forms saidcarbon-doped silicon oxide layer.
 16. The method of claim 13 whereinsaid first temperature is between 55 and 100° C.
 17. The method of claim14 wherein said second temperature is chosen to inhibit a reaction ofsaid process gas within said lid.
 18. The method of claim 17 whereinsaid second temperature is approximately 25° C.
 19. The method of claim14 wherein the substrate is heated by a pedestal heater set to atemperature of between 150-200° C.
 20. The method of claim 14 whereinthe organosilane precursor is either tetramethylsilane ortrimethylsilane.
 21. A computer readable storage medium having acomputer-readable program embodied therein for directing operation of asubstrate processing system including a process chamber having walls anda lid; a substrate holder; a heater, operatively coupled to heat saidsubstrate holder; a gas delivery system configured to introduce gasesinto said process chamber, a first heat exchanger operatively coupled tosaid walls, a second heat exchanger operatively coupled to said lid;said computer-readable program including instructions for operating saidsubstrate processing system to form an insulation layer over a substratedisposed in the processing chamber in accordance with the following:flowing a process gas comprising ozone and an organosilane into thesubstrate processing chamber; heating the substrate to a temperature ofless than about 250° C. to form a carbon-doped silicon oxide layer overthe substrate; densifying said carbon-doped silicon oxide layer;maintaining the walls at a first temperature; and maintaining the lid ata second temperature.